JPH0350757B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel organophosphorus compound that exhibits an effective control action against harmful insects, mites, and nematodes, and insecticides and acaricides containing the compound as an active ingredient.
Regarding nematicides. The compound of the present invention is a novel organic phosphorus compound represented by the following general formula (), and includes stereoisomers and optical isomers. In the formula, X and Y are a methyl group, a phenyl group, or a 4-
It is a chlorophenyl group (however, one is a methyl group and the other is a phenyl group or a 4-chlorophenyl group), Z ¹ and Z ² are oxygen atoms or sulfur atoms, and R ¹ and R ² are alkyl groups. be. The alkyl groups represented by R ¹ and R ² in the general formula () include methyl, ethyl, propyl,
Examples include butyl. The compound of the present invention can be produced, for example, by the following method. (In the formula, HAL is a halogen atom, and X, Y, Z ¹ ,
Z ² , R ¹ and R ² are as described above. ) The reaction is usually carried out at -100 to 50°C, preferably at -
It is carried out at a temperature range of 80-20°C. In addition, this reaction is carried out in the presence of an acid acceptor, and acid acceptors include organic lithium compounds such as n-butyllithium and phenyllithium, inorganic bases such as potassium hydroxide and sodium hydride,
Examples include organic bases such as triethylamine and pyridine. Furthermore, these reactions are preferably carried out in the presence of a solvent, and examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or acyclic aliphatic hydrocarbons such as hexane and cyclohexane; Ethers such as diethyl ether, methyl ethyl ether, dioxane, and tetrahydrofuran; Nitriles such as acetonitrile, propionitrile, and acrylonitrile; and aprotic polar solvents such as dimethyl sulfoxide and sulfolane. Synthesis Example 1 Synthesis of trans-4-(4-chlorophenyl)-5-methyl-3-(0-ethyl-S-n-propylthiophosphoryl)-2-thiazolidone (1) Erythro-1-amino-2-( 9.3 g of 4-chlorophenyl)-propyl sulfate was suspended in 60 ml of ethanol, and 5.4 g of carbon disulfide was added thereto.
After gradually dropping 40 ml of an aqueous solution containing 4.4 g of potassium hydroxide, the mixture was reacted at 40° C. with stirring for 3 hours. After the reaction is complete, ethanol is distilled off under reduced pressure.
The extract was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 5.0 g of trans-4-(4-chlorophenyl)-5-methylthiazolidine-2-thione. (2) Trans-4-(4-chlorophenyl)-5-methylthiazolidine-2 obtained by the reaction in (1) above
- Dissolve 5.0 g of thione in 50 ml of methanol,
30 g of methanol solution containing 5.35 g of sodium methoxide was added thereto. Next, 10.7 g of 30% hydrogen peroxide solution was gradually added dropwise at a temperature below 40°C, and the mixture was allowed to react at room temperature for 1 hour with stirring. After the reaction, methanol was distilled off under reduced pressure, extracted with ethyl acetate, the extracted layer was washed with water, dried over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure to obtain trans-4-(4-chlorophenyl)-5-methyl-2 with a melting point of 119-121°C.
- 1.8 g of thiazolidone was obtained. (3) Dissolve 0.8 g of trans-4-(4-chlorophenyl)-5-methyl-2-thiazolidone obtained in the reaction in (2) above in 20 ml of tetrahydrofuran,
Cooled to -78°C. 2.3 ml of a hexane solution (1.65 M) of n-butyllithium was gradually added dropwise thereto, followed by stirring for 30 minutes. Then, 0-ethyl-
5 ml of a tetrahydrofuran solution containing 0.78 g of S-n-propylthiophosphoric acid chloride was gradually added dropwise, stirred for 30 minutes, and then reacted at room temperature for 3 hours. After the reaction was completed, the product was poured into ice water and added to ethyl acetate. The extract layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure and purified by silica gel column chromatography to obtain 0.5 g of the target product with a refractive index of 1.5426 (24.6°C). Synthesis Example 2 Synthesis of trans-5-(4-chlorophenyl)-4-methyl-3-(0-ethyl-S-n-propylthiophosphoryl)-2-thiazolidone trans-5-(4-chlorophenyl)-4- 1.0 g of methyl-2-thiazolidone was dissolved in 20 ml of tetrahydrofuran and cooled to -78°C. Add n-butyllithium hexane solution (1.65M)
After gradually dropping 3.2 ml, the mixture was stirred for 30 minutes. Next, 5 ml of a tetrahydrofuran solution containing 1.0 g of 0-ethyl-S-n-propylthiophosphoric acid chloride was added.
was gradually added dropwise, stirred for 30 minutes, and then reacted at room temperature for 3 hours. After the reaction, the product was poured into ice water and extracted with ethyl acetate. The extracted layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and purified by silica gel column chromatography. 1.0 g of the target product with a yield of 1.5592 (27.6°C) was obtained. Typical specific examples of the compounds of the present invention produced by the above-mentioned Synthesis Examples 1 and 2 or by general production methods are shown below. Compound No. 1 trans-5-(4-chlorophenyl)-4-methyl-3-(0-ethyl-S-n-
Propylthiophosphoryl)-2-thiazolidone
n _D 1.5592 Compound No. 2 trans-5-(4-chlorophenyl)-4-methyl-3-(0,0'-diethylphosphoryl)-2-thiazolidone n _D 1.5430 Compound No. 3 trans-5-(4- chlorophenyl)-4-methyl-3-(0,0'-dimethylthiophosphoryl)-2-thiazolidone n _D 1.5904 Compound No. 4 trans-4-(4-chlorophenyl)-5-methyl-3-(0-ethyl -S-n-
Propylthiophosphoryl)-2-thiazolidone
n _D 1.5426 Compound No. 5 trans-5-phenyl-4-methyl-3-(0-ethyl-S-sec-butylthiophosphoryl)-2-thiazolidone n _D 1.5550 The compound of the present invention is as shown in the test example below. , exhibits excellent activity as an active ingredient in insecticides, acaricides, and nematicides. For example, plant parasitic mites such as two-spotted spider mite, false red spider mite, orange spider mite, etc., ectoparasitic mites such as house dust mite, diamondback moth, armyworm, fall armyworm, Colorado potato beetle, rainbow ladybug, peach aphid, black leafhopper, yellow leafhopper, Agricultural pests such as the onion fly, scarab beetles, and cutworms, sanitary pests such as cockroaches, houseflies, Culex mosquitoes, termites, etc., grain storage pests such as azuki bean paramecium, small beetles, etc., clothing such as cutworms, etc. pests,
It is also effective against fleas, lice, flies, etc. that parasitize livestock, etc., and is also effective against plant parasitic nematodes such as cat nematodes, cyst nematodes, Negusare nematodes, rice heart blight nematodes, etc. It is also effective against sex nematodes. It is also effective against plant parasitic mites that are resistant to Dicofol and organophosphates. When using the compound of the present invention as an active ingredient in insecticides, acaricides, and nematicides, it can be used in emulsions, powders,
It can be formulated into various forms such as wettable powders and liquid preparations. When actually using these preparations,
It can be used as is, or diluted with water or the like to a predetermined concentration. The pesticide adjuvants mentioned here include solid carriers such as talc, kaolin, bentonite, diatomaceous earth, white carbon, clay, and starch, and liquid dilutions such as water, toluene, xylene, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, and alcohol. Agents, emulsifiers, dispersants, spreading agents, etc. can be mentioned. In addition, if necessary, it can be mixed or used in combination with other agricultural chemicals, such as insecticides, acaricides, nematicides, fungicides, plant growth regulators, etc. In this case, even better effects can be obtained. There is also. For example, insecticides or acaricides include organophosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organochlorine compounds, dinitro compounds, organosulfur or organometallic compounds, and antibiotics. , substituted diphenyl ether compounds, urea compounds, triazine compounds, benzoyl urea compounds, and birethroid compounds.
-(2,3-difluorobenzoyl)-N'-(p-
chlorophenyl)urea, N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-
Benzoyl urea compounds such as (3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl urea, pyrethroids such as α-cyano-3-phenoxybenzyl-2-(4-chlorophenyl)isovalerate Examples include type compounds. The insecticide, acaricide, and nematocide of the present invention are effective for controlling various harmful insects, harmful mites, and harmful nematodes, and the application amount is generally 1 to 10,000 ppm, preferably 20,000 ppm.
Perform at an active ingredient concentration of ~2000 ppm. In the case of harmful aquatic insects, it is possible to control them by spraying a chemical solution in the above concentration range to the place where they occur, so it is effective even if the concentration range of the chemical solution in water is less than the above range. Test Example 1 Each formulation of active ingredient compound was dispersed in water and adjusted to a predetermined concentration. A cutlet (7 cm in diameter,
The seedlings were transplanted to a height of 4 cm) and inoculated with approximately 30 young adult mites. This product was immersed in the chemical solution adjusted to the predetermined concentration for about 10 seconds, air-dried, and then left in an illuminated incubator at 28°C. On the second day after the release of the insects, whether the insects were alive or dead was determined, and the mortality rate was calculated using the following calculation formula, and the results shown in Table 1 were obtained. Mortality rate (%) = Number of dead insects / Number of released insects x 100

[Table] Test Example 2 Cabbage leaf pieces were immersed for about 10 seconds in a drug solution in which each active ingredient compound was dispersed in water and adjusted to a predetermined concentration, and then air-dried. A Petri dish with a diameter of 9 cm was lined with wet paper, and air-dried leaf pieces were placed on top of it. 2nd to 3rd instar diamondback moth larvae were released into the container, the container was covered with a lid, and the container was left in a lighted incubator at 26°C. On the second day after the insects were released, whether they were alive or dead was determined, and the mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 2 were obtained.

[Table] Test Example 3 The test was carried out in the same manner as in Test Example 2 above, except that the 2nd to 3rd instar diamondback moth was replaced with the 2nd to 3rd instar Spodoptera japonica, and the results shown in Table 3 were obtained.

[Table] Test Example 4 A kidney bean with only one primary leaf left was transplanted into a cup, inoculated with adult two-spotted spider mites to lay eggs, and the adult was removed. Next, the kidney beans were immersed in a drug solution containing the active ingredient compound dispersed in water and adjusted to a predetermined concentration for about 10 seconds, air-dried, and then left in an illuminated incubator at 28°C. After 5 days, the hatching status of the eggs was investigated, and the ovicidal rate was calculated using the following calculation formula, and the results shown in Table 4 were obtained. Egg killing rate (%) = Number of eggs killed / Number of eggs laid x 100

[Table] Test Example 5 10 rice seedlings were added to a chemical solution adjusted to a concentration of 800 ppm.
After soaking for a second and air drying, the roots were wrapped with absorbent cotton and placed in a test tube. Next, 10 adult brown planthoppers were released into the tube, and the mouth of the tube was covered with gauze. 2
After a day, the insects were examined to see if they were alive or dead, and the insect mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 5 were obtained.

[Table] Test example 6 Nekobu contaminated soil was packed in a 1/5000 are pot,
Tomato seedlings at the 3- to 4-leaf stage were irrigated with a prescribed amount of a chemical solution adjusted to contain 250 g/a of the active ingredient. Two days after the chemical treatment, tomato seedlings at the 3- to 4-leaf stage were transplanted, and 20 days after the chemical treatment, the degree of catbulation was investigated. The results shown in Table 6 were obtained. The degree of cat-bub settlement was determined according to the following criteria: 0 No cat-bub settlement 1 〃 Few 2 〃 Medium 3 〃 Many 4 〃 Very large

[Table] Test Example 7 Cabbage leaf pieces were immersed for about 10 seconds in a drug solution containing each active ingredient compound dispersed in water and adjusted to a concentration of 800 ppm, and air-dried. Diameter 9cm
A Petri dish was lined with wet paper, and air-dried leaf pieces were placed on top of it. Wingless viviparous female green peach aphids were released there, the lid was placed, and the container was left in a lighted incubator at 26°C. On the second day after the insects were released, whether they were alive or dead was determined, and the mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 7 were obtained.

[Table] Test Example 8 Each formulation of active ingredient compound was dispersed in water and adjusted to a predetermined concentration. A cutlet (7 cm in diameter,
Approximately 30 young adult spider mites resistant to dicofol and organophosphorus were inoculated onto the transplanted plants to a height of 4 cm). This product was immersed in the chemical solution adjusted to the predetermined concentration for about 10 seconds, air-dried, and then left in an illuminated incubator at 28°C. On the second day after the insects were released, whether they were alive or dead was determined, and the mortality rate was determined in the same manner as in Test Example 1.
Obtained the results in the table.

[Table] Test Example 9 A kidney bean with only one primary leaf left was transplanted into a cup, inoculated with adult two-spotted spider mites resistant to dicofol and organophosphorus, allowed to lay eggs, and the adult was removed. Next, the kidney beans were immersed in a drug solution containing the active ingredient compound dispersed in water and adjusted to a predetermined concentration for about 10 seconds, air-dried, and then left in an illuminated incubator at 28°C. After 5 days, the hatching status of the eggs was investigated, and the ovicidal rate was determined in the same manner as in Test Example 4, and the results shown in Table 9 were obtained.

[Table] Test Example 10 A cup (diameter 7 cm, height 4 cm) was filled with powdered feed (product of Oriental Yeast Co., Ltd.) as a medium for house fly larvae, wheat bran, and a chemical solution adjusted to a concentration of 200 ppm at a weight ratio of 1:1. A mixture of 2:2 was added. Second to third instar housefly larvae were released into the container, covered with gauze, and left there. After releasing insects
On the 12th day, the survival of the larvae was investigated, and the mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 10 were obtained.

[Table] Test Example 11 40g of air-dried soil was placed in an ice cream cup, and 10ml of the chemical solution adjusted to a concentration of 200ppm was poured into it and mixed uniformly. After 24 hours of mixing, onion pieces were buried in the soil as bait, and 10 onion flies were placed there.
Ten day-old larvae were released. After 48 hours, the insects were examined to see if they were alive or dead, and the insect mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 11 were obtained.

[Table] Formulation example 1 (a) Compound No. 1 20 parts by weight (b) N,N'-dimethylformamide 70 parts by weight (c) Polyoxyethylene alkyl phenyl ether 8 parts by weight. It was dissolved to form an emulsion. Formulation Example 2 (a) Compound No. 3 5 parts by weight (b) Talc 95 parts by weight The above ingredients were uniformly mixed and dissolved to form a powder. Formulation example 3 (a) Compound No. 4 50 parts by weight (b) Fine powder silica 15 parts by weight (c) Fine powder clay 25 parts by weight (d) Naphthalenesulfonic acid soda formalin condensate 2 parts by weight (e) Dialkyl sulfosuccinate 3 Parts by weight (f) Polyoxyethylene alkyl allyl ether sulfate 5 parts by weight The above components were uniformly ground and mixed to prepare a wettable powder. Formulation example 4 (a) Compound No. 5 5 parts by weight (b) Bentonite 45 parts by weight (c) Kaolin 50 parts by weight The above ingredients were kneaded with a small amount of water, extruded into granules, and dried to form granules. .

Claims (1)

[Claims] 1. General formula [In the formula, X and Y are a methyl group, a phenyl group, or a 4-
It is a chlorophenyl group (however, one is a methyl group and the other is a phenyl group or a 4-chlorophenyl group), Z ¹ and Z ² are oxygen atoms or sulfur atoms, and R ¹ and R ² are alkyl groups. An organic phosphorus compound represented by 2 General formula [In the formula, X and Y are a methyl group, a phenyl group, or a 4-
It is a chlorophenyl group (however, one is a methyl group and the other is a phenyl group or a 4-chlorophenyl group), Z ¹ and Z ² are oxygen atoms or sulfur atoms, and R ¹ and R ² are alkyl groups. An insecticide, acaricide, or nematocide containing as an active ingredient at least one type of organophosphorus compound represented by the following.